Two phase fast breaking foam pressurized hair waving composition



United States Patent 3 433,868 TWO PHASE FAST BREAKING FOAM PRES-SURIZED HAIR WAVING COMPOSITION Stanley Brechner, West Orange, MeyerMalakolf, Kendall Park, and Martin M. Rieger, West Englewood, N.J.,

assignors to Warner-Lambert Pharmaceutical Company,

Morris Plains, N.J., a corporation of Delaware No Drawing. Filed July27, 1964, Ser. No. 385,467 US. Cl. 424-47 Claims Int. Cl. A61k 7/10ABSTRACT OF THE DISCLOSURE An improved two liquid phase pressurized hairwaving composition adapted for discharge from its container as a foam,consisting of a low molecular weight mercaptoalkanoic acid, analkalizing agent imparting to the composition a pH of above about 7, apropellant, a surface active agent, a polyhydric alcohol, and thebalance substantially water.

This invention relates to improved liquid cold waving preparationspackaged in pressurized containers for use in the permanent waving ofhair. More particularly, the present invention relates to a compositionfor use in the cold permanent waving of hair which upon release from apressurized container forms a fast breaking foam.

Cold permanent waving compositions are well known to the art. Thesecompositions accomplish the permanent waving of hair through theirability to break the disulphide bonds of the cystine, which is a majorconstituent of the keratin of hair, and on the successive transformationof the cystine to cysteine. When the disulphide bonds are broken, thehair tresses become pliable and easily shaped to a new configuration.Upon regeneration of the disulphide bond and conversion from cysteine tocystine by oxidation, the hair tresses then become permanently fixed inthe shape of the new configuration. The means used for breaking thedisulphide bonds of cystine by chemical agents are numerous with themost widely used and preferred agents being mercaptans such asthioglycolic acid.

Cold permanent waving compositions are usually applied to the hair withcotton pads or small sponge applicators by repeatedly saturating theapplicator with the hair waving lotion and thereafter transferring thelotion from the applicator on to the hair. This method is recognized asbeing cumbersome, tedious and time-consuming with irritation ofsensitive skin resulting on prolonged contact with the lotion. Inaddition, little control is possible through the use of suchapplicators.

The use of plastic squeeze bottles and special hair combs have beenproposed to overcome the many problems which exist in the application ofcold permanent waving lotions to the hair, but these devices do notmaterially overcome the deficiencies inherent in the conventionalapplicators.

The volatility and susceptibility to oxidation of the active ingredientsin hair waving lotions make ordinary methods of packaging inappropriate.Once the containers of permanent hair waving lotion are opened to theatmosphere, they cannot be stored and used repeatedly without loss ofactivity. One type of packaging which enables alternate use and storagesuch as is required for touch-up waves as well as for periodic fullwaving is the aerosol package.

Aerosol packages or pressurized containers have been widely employed forpackaging many products for household purposes. In spite of theirrecognized advantages in other areas, aerosol packaging techniques havenot been widespread for application of cold permanent waving 3,433,868Patented Mar. 18, 1969 compositions. The usual aerosol methods whichmight be used to dispense hair waving products such as foams or mistsare by their very nature less able to meet the demands of cold waving ofhair than are the conventional application techniques. A foam, forexample, acts as a physical impediment to the penetration of thereducing agent into the hair, whereas a mist is unsatisfactory becauseof the wide diffusion of the hair lotion, with the outside of a woundtress receiving a heavy concentration of the lotion, while the portionof the hair inside a wound curl may receive a much smaller amount. As aresult, portions of the hair may be damaged by over concentration withlotion, while other parts of the wound curl may not be reduced at allbecause of insuflicient contact by a sufficient amount of lotion whichis ordinarly neces sary to break the disulphide bonds. In order then toprovide a suitable pressurized cold permanent hair waving composition inan aerosol package, the composition should neither be expelled as aspray nor as a stable foam. It has now been recognized that the problemof providing a pressurized cold permanent waving composition may beovercome by use of a hair waving composition which is dispensed from anaerosol container as a foam which collapses to a liquid promptly afterdischarge and which is capable of being absorbed by the hair at aboutthe same rate as the foam collapses to a liquid.

In order to achieve aerosol permanent waving compositions which collapseas a fast breaking foam, a series of important criteria must be met. Oneis that the cold permanent hair waving composition should containpropellants which are finely dispersed throughout the composition. Atrue solution or a molecular dispersion is found to be ideal. However,many propellants known and available for use in propelling cold wavingcompositions are generally not very soluble in aqueous solutions,particularly those containing keratin-reducing agents. Mutual solventssuch as alcohols can be employed to overcome this problem, but thesecompositions are generally less effective in the cold permanent wavingof hair. In addition, the alcohol which is required adds to the cost ofthe final composition.

Use of two liquid phase compositions in pressurized packages is wellknown and may be recognized in the teaching of Baton, US. Patent No.2,728,495, wherein there is disclosed a composition having an aqueousliquid phase which floats on top of a liquid propellant phase. Thiscomposition does not discharge as a foam although it can be dischargedas a foam after violent agitation.

It has now been found that the disadvantages heretofore encountered inconveniently applying cold permanent Waving compositions to the hair maynow be overcome by providing a two-phase permanent waving compositioncontaining a keratin-reducing agent in one phase and a liquefiedpropellant in the second phase such that the hair waving composition maybe discharged from a container as a foam which collapses to a liquidpromptly upon discharge.

It is an object of this invention, therefore, to provide a coldpermanent waving composition packaged in pressurized containers for usein improving methods of cold permanent waving of hair.

It is also an object of this invention to provide a two liquid phasecomposition dischargeable as a fast breaking foam for use in coldpermanent waving hair upon release from a pressurized container.

It is also an object of this invention to provide a pressurized coldpermanent hair waving composition which can be used and then stored forsubsequent application without material loss of activity between uses.

It is a further object of this invention to provide an improved methodof permanent waving of hair with a cold permanent waving compositionwhich eliminates or greatly reduces the possibility of skin irritationwhich may otherwise result when a liquid waving lotion is applied to thehair in an amount greater than may be absorbed.

Other objects and advantages will appear from the following detaileddescription.

Generally, the present invention comprises an improved hair wavingprocedure and composition packaged in a pressurized container such thatthe composition may be released as a fast-breaking foam whichsubstantially breaks or collapses into a liquid promptly upon dischargefrom the container. The application of an unstable foam waving lotion tothe hair eliminates run off because the foam collapses to a liquid atabout the same rate the liquid is absorbed into the hair tresses.

The cold permanent hair waving compositions of this invention generallycomprises an aqueous solution of a keratin-reducing agent, a liquefiedpropellant, and at least one surface active agent packaged in a suitablepressurized container. Particular polyhydric alcohols can also beincluded and have been found to provide improved hair wavingcharacteristics to the composition. When maintained in a package underpressure, the present composition exists as two liquid phases and avapor phase. Upon discharge from the container, the composition forms afoam which is unstable and which substantially completely collapses to aliquid within a very short time after discharge.

The keratin-reducing compounds desirably employed as agents for reducingthe cystine to cysteine by rupture of the keratin disulphide bonds inthe present cold permanent waving composition include low molecularweight watersoluble mercaptans containing as functional groups, inaddition to the mercaptan group present, radicals SIlCth as carboxyl,hydroxyl or amide. The mercapto-alkanoic acids described by McDonough inUS. Patent No. 2,577,710 are effective keratin-reducing agents for useherein with thioglycolic acid being preferred. Mercaptopropionic acid isalmost equally suitable as are ammonium thioglycolate, thioglycerol andthe like.

It is desirable to have the pH of the waving lotion above pH 7 to obtainrapid and effective action and to have the pH below 10 to avoid hairdamage. A particularly desirable range is from pH 8.5 to pH 9.6. A pH ofabout 9.3 is especially suitable. Although it is recognized that anysuitable alkali may be used to adjust the pH within the indicated range,it is preferred to use a weak base or a mixture of bases containing atleast one weak base as the alkali to provide a buffering and hairswelling effect. Suitable weak bases having dissociation constants ofless than 10" and preferably less than 10 are useful and includecompounds such as ammonia, monoethanolamine, diethanolamine,tris(hydroxymethyl) aminomethane and 3- amino 2 methyl 1,3 propanediolwith ammonia being preferred.

When the pH of the hair waving lotion is adjusted in the preferred rangewith a Weak base, there will usually be present free base in excess ofthat required to form the salt of the mercapto-alkanoic acid. Strongbases may also be used in conjunction with a weak base to form thesesalts. Examples of strong bases useful in this invention include sodiumhydroxide, lithium hydroxide, potassium hydroxide, and strong organicbases such as tetramethylammonium hydroxide. Soluble canbonates andbicarbonates such as the ammonium salts may also be added for their pHstabilizing effect. Use of a thioglycolate salt in preparing the wavinglotion is, of course, equivalent to preparing it in situ fromthioglycolic acid and the appropriate base.

The keratin-reducing agent may be incorporated into the lotion at alevel equivalent to from 1 to about weight per cent, based on the totalcomposition of thioglycolic acid.

The propellant required to force the hair waving composition from thepressurized container may be any liquefiable gas or combination ofliquefiable gases having a suitable vapor pressure, but certainhalogenated hydrocarbons are preferred for use in this invention.

The halogenated hydrocarbon propellants are the fluorinated, andchlorinated-fluorinated low molecular weight saturated aliphatichydrocarbons which may be represented generally by the formula C H Cl Fwherein n is a whole number (usually 1 or 2), x is zero or a .wholenumber, y is zero or a whole number, and z is a whole number, and thesum of x, y, and z is equal to 212+2. Examples of useful propellantstaken either alone or in combination include monochlorotrifluoromethane,trichloromofluoromethane, dichlorodifluoromethane,dichloromonofiuoromethane, monochlorodifluoromethane,trichlorotrifluoroethane, dichlorotetrafluoroethane, difiuoroethane, anddifluromonochloroethane.

The amount of propellant which may be employed depends upon thepropellant chosen, the other ingredients of the composition and thedesired pressure in the package. Desirably, from about 2 weight percentto about 20 weight percent propellant may be employed. The usual amountof propellant employed is in the range of 2.5% to 15% by weight andpreferably about 6% to about 8% by weight.

A sunface active agent is included in the compositions of thisinvention. Its presence within prescribed limits enables the dischargeof a suitable foam. If too much surface active agent is employed in thecomposition, the foam tends to break too slowly. Enough surface activeagent must be used to achieve a desirable but fast breaking foam. Foruse herein, the term fast breaking is intended to mean a foam whichbreaks or collapses to a liquid in less than 40 seconds and preferablyin about 2 to about 10 seconds after discharge on the hair.

Suitable sunface active agents maybe found among the anionic detergents,and among nonionic detergents.

In the case of anionic detergents, it is preferred that the cation ofthe detergent be one which confers high solubility on the detergent. Thechoice of a surface active agent is not critical with most of thosecommonly employed in shampoos and other personal detergent productsbeing satisfactory. Examples of anionic synthetic detergents suitablefor use in the practice of this invention include detergents of thesulfonated and sulfated types such as the alkyl (Cg-C13) sulfates, thealkyl (Cg-C18) polyethenoxy (l-10 units of C H O) ether sulfates, themonoor di-alkyl (Cg-C13) esters of sulfosuccinic acid, sulfonated orsulfated amides of higher fatty acids, sulfuric acid esters ofpolyhydric alcohols incompletely esterified with higher fatty acids,higher fatty acid esters of low molecular weight alkylol sulfonic acids,etc., usually in the form of their sodium, potassium, ammonium, oralkanolammonium salts. Some of the particular detergents within thisuseful category include sodium octyl sulfate, sodium nonyl sulfate,sodium decyl sulfate, monoethanolammonium dodecyl sulfate, ammoniumtetradecyl sulfate, monoethanolammonium pentadecyl sulfate,monoethanolammonium hexadecyl sulfate, monoethanolammonium octadecylsulfate, monoethanolammonium oleyl sulfate, sodium salts of dioctylsulfosuccinate, sodium salts of the oleic acid ester of isethionic acid,sodium salt of the lauric acid amide of taurine, triethanolammoniumcoconut oil monoglyceride monosulfate, monosulfate, monoethanolammoniumtallow diglyceride monoethanolammonium tallow diglyceride monosulfate.Mixtures of these various anionic surface active agents are also usefuland include those which come within the scope of the general classdefinition.

Water soluble soaps of fatty acids, such as sodium, potassium, ammoniumor triethanolamine salts of tallow or coconut oil fatty acid, may beused, but the synthetic detergents are preferred. When waving lotioncontaining soap is rinsed from the hair with hard water, soap curd mayform and be left as a dulling film on the hair. Synthetic detergents aregenerally free of this disadvantage.

Water soluble nonionic synthetic organic detergents are wherein Rrepresents long chain alkyl radicals having from about 8 to about 18carbon atoms and n is an integer from about 4 to about 30; thepolyethylene oxide condensates of alkyl phenols, e.g., the condensationprodnets of alkyl phenols having about 6 to 12 carbon atoms in the alkylgroup, in either straight chain or branched chain configuration, withethylene oxide in amounts equal to 2 to 25 moles of ethylene oxide permole of alkyl phenol; compounds formed by condensing ethylene oxide witha hydrophobic base formed by the condensation of propylene oxide withpropylene glycol; the condensation product of ethylene oxide with theproduct resulting from the reaction of propylene oxide and ethylenediamine. Compounds with ether linkages are preferred because of theirresistance to hydrolysis in alkaline solutions.

Specific compounds commercially available for use herein include, forexample, Brij 30 (polyoxyethylene (4) lauryl ether by Atlas ChemicalIndustries of Delaware), Brij 35 (polyoxyethylene (23) lauryl ether alsoby Atlas), Brij 72 (polyoxyethylene (2) stearyl ether by Atlas), Brij 76(polyoxyethylene stearyl ether by Atlas), Brij 76 (polyoxyethylene (20)stearyl ether by Atlas), Brij 52 (polyoxyethylene (2) cetyl ether byAtlas), Brij 56 (polyoxyethylene (10) cetyl ether by Atlas), and Brij 58(polyoxyethylene (20) cetyl ether by Atlas). In addition, surface activeagents such as Duponol WAQ (a lauryl alcohol sulfate sodium saltcomposition by Dupont of Delaware), Ethomid HT- hydrogenated tallowamide containing 5 moles ethylene oxide (a fatty acid amide-ethyleneoxide condensate by Armour & Company of Illinois), G-1441 (apolyoxyethylene sorbitol lanolin derivative by Atlas Powder Company ofDelaware), G-3910 (a polyoxyethylene oleyl alcohol derivative also byAtlas Powder Company), Emulphor ON-870 (a polyoxyethylene cetyl oleylalcohol by Antara Chemicals of New York), Siponic Y-100 (apolyoxyethylene oleyl alcohol by Alcolac Chemical Company of Maryland),Siponic Y-500 (a polyoxyethylene oleyl alcohol also by Alcolac), SiponicCD (polyoxyethylene (C branched chain) alcohols by Alcolac), andEthoxylan 100 (a polyoxyethylene lanolin alcohol by Malmstrom ChemicalCompany of New York), and Lanogel 31 (a polyoxyethylene lanolinderivative by Robinson Wagner) may also prove useful.

G1441 is composed of 65.1 percent ethylene oxide, 6.7 percent sorbitoland 28.2 percent lanolin by weight (Drug and Cosmetic Industry, June1957, p. 846). Langel 31 has an iodine value of 4-12 (Hanus), is watersoluble and has a saponification value of 9-18 (American Per furner andCosmetics, March 1964, p. 51). Emulphor ON-870 has a HLB value of 15.4(Journal of Pharmaceutical Sciences, September 1961, p. 734). G-3910contains ethylene oxide units (Journal of Pharmaceutical Sciences,September 1961, p. 734). Duponol WAQ and Ethomid HT-15 are identified inDetergents and Emulsifiers 1963 Annual.

The quantity of surface active agent employed in the present compositionis from about 0.05% to about 3 /2% by weight. The surface active agentserves the primary purpose of contributing to the production of a foamhaving the desired characteristics; it also aids in solubilizing oremulsifying the perfume and contributing to the dispersion of thepropellant.

Certain polyhydric alcohols are preferably added to the present hairwaving composition as they greatly improve the Waving characteristics ofthe expelled foam. These alcohols are usefully employed in an amount ofabout 0.5% to about 5% by weight, based on the total amount of the hairWaving phase. Useful compounds include polyhydric alcohols such asglycerine and glycols such as 1,3-butylene glycol, propylene glycol,1,2,6- hexanetriol, 1,5-pentanediol, polyethylene glycol 200,polyethylene glycol 400, polyethylene glycol 600, tetraethylene glycol,triethylene glycol, dipropylene glycol, polypropylene glycol 150,tripropylene glycol, Z-methyl pentanediol-2,4, 2-ethyl hexanediol-1,3,and the like. 1,3- butylene glycol and Z-methyl pentanediol-2,4 arepreferred.

Various minor ingredients can be included in the compositions of thisinvention and are generally desirable for the purposes of making theproduct more pleasant to use and leaving the hair in a particularly goodcondition. It is generally also recognized that it is possible toinclude a soluble salt of the disulphide of the keratin-reducing agent,especially the disulphide of the thioglycolic acid, at a level, based onthe total composition, equivalent to form about 0.5% to 5% ofdithiodiglycolic acid. The soluble salts which can be used include thoseformed from the bases listed as suitable for making the pH adjustment.These additives protect the hair from over-treatment and leave it in aparticularly good condition as is disclosed in US. Patents 2,719,814 and2,719,815. A perfume will be added in the preferred compositions of thisinvention.

The compositions of this invention must be packaged in suitablepressure-tight containers. For pressures lower than about 25 p.s.i.g. at70 F., glass bottles, which may be coated on the outside with plastic,and metal cans are suitable. Metal cans are preferably employed forhigher pressures. A metal which is not appreciably corroded :by theproduct should be chosen and/or a corrosion inhibitor should be added tothe formulation. Aluminum cans are preferred because of their lightness,economy and resistance to corrosion. When aluminum cans are used, it isparticularly desirable to include in the waving lotion, as a corrosioninhibitor, from about 0.001% to about 0.1% SiO as water soluble sodiumsilicate. Water soluble sodium silicates having a weight ratio of SiO-:Na O in the range of about 5:1 to about 1:1 are quite satisfactory.

The valves with which the pressurized containers are fitted to controltheir opening and discharge of product, are those commercially employedfor other aerosol products. Nozzles for discharge of the product are notcritical except that it is preferred to use a foam type nozzle. Thistype of nozzle provides opportunity for an appreciable pressure dropwhile the product is still confined within the nozzle. This pressuredrop within the enclosed channel permits the foam to be generated withinthe nozzle. Foam nozzles are commercially available and have beenrepeatedly described in the literature. For example, the US. Patent2,655,480 of Spitzer et al. shows a typical foam nozzle.

The following examples are set forth to further illustrate the practiceof the present invention.

Example 1 The following composition is prepared and introduced intopressurized plastic-covered bottles fitted with valves to control thedischarge of the product.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.40 Sodiumhydroxide 0.39 Ammonia solution (28%) 6.05 Polyoxyethylene cetyl oleylalcohol (Antara Chemicals Emulphor ON870) 1.30

Ingredients: Percent by weight Polyoxyethylene (l) oleyl alcohol (AtlasChemicals G-39l0) 0.18 Polyoxyethylene sorbitol lanolin derivative(Atlas Chemicals Gl44l) 0.09 Propylene glycol 1.25 Sodium lauryl sulfatepaste (Duponts Duponol WAQ) 1.00 Perfume 0.45 Dichlorodifiuoromethane1.00

Dichlorotetrafluoroethane 9.00 Distilled water Balance Perfume whilehaving a desirable effect on the product is not essential to the successof the present invention. When packaged, this composition is found togive a pressure of about 25 p.s.i.g. at 70 F. and when used in wavinghair, the composition is easy to apply to the hair without run off ofexcess lotion.

Monoethanolamine, tris(hydroxymethyl) aminomethane,2-amino2-methyl-1,3-propanediol and diethanolamine can replace ammonia,in whole or in part, and pH adjustment can be from pH 8.5 to pH 9.6 inthis example without losing its advantages.

Example 2 The following composition is prepared and introduced intopressurized plastic-covered glass bottles fitted with valves to controlthe discharge of the product.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.65 Sodiumhydroxide 0.41 Ammonia solution (28%) 6.25 Polyoxyethylene cetyl oleylalcohol (Antara Chemicals Emulphor ON-870) 2.10

Polyoxyethylene oleyl alcohol (Atlas Chemicals G3910) 0.28Polyoxyethylene lanolin alcohol (Malmstrom Ethoxylan 100) 0.19 2-methylpentanediol-2,4 2.15 Perfume 0.45 Dichlorodifiuoromethane 2.00Dichlorotetrafluoroethane 5.00 Distilled water Balance When the abovecomposition is used in waving hair, very satisfactory results arerealized as is the advantage that the preparation is easy to applyneatly to the hair without run off of excess lotion.

Example 3 The following composition is prepared and packed in apressurized aluminum can fitted with a valve to control discharge of theproduct with a foam nozzle.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.65 Sodiumhydroxide 0.41 Ammonia solution (28%) 6.25

Polyoxyethylene oleyl alcohol (Alcolac Chemicals Siponic Y-lOO) 0.28Polyoxyethylene oleyl Alcohol (Alcolac Chemicals Siponic Y-500) 2.10Polyoxyethylene lanolin alcohol (Robinson Wagner's Lanogel 31) 0.191,3-butylene glycol 1.80 Sodium silicate (Na O:SiO ratio of 3.22:1) 0.08Perfume 0.45 Monochlorodifiuoroethane 3.40 Difiuoroethane 3.40 Distilledwater Balance Perfume and sodium silicate while having a desirableeffect on the product are not essential to the success thereof. When thecomposition is used in waving hair, satisfactory results are noted as isthe advantage that the composition is easy to apply to the hair withoutrun off of excess lotion.

Monoethanolamine, tris(hydroxymethyl) aminomethane,2-amino-2-methyl-1,3-propanediol and diethanolamine can replace ammonia,in whole or in part, and pH adjustment can be from pH 8.5 to pH 9.6 inthis example without losing its advantages.

Example 4 The following composition is prepared and packed in apressurized aluminum can fitted with a valve to con trol the dischargeof the product with a foam nozzle.

When packaged in aerosol form, the vapor pressure of the composition isfound to be about 55 p.s.i.g. at 70 F. When discharged, the compositionappears as a foam which substantially collapses to a liquid within about20 seconds. The propellant is found to float on the aqueous phase onprolonged standing but upon shaking is readily redispersed. When thecomposition is used in waving hair, very satisfactory results arerecognized over leading commercial waving preparations. The compsitionhas ing commercial waving preparations. The composition has without runoff of excess lotion.

Example 5 The following composition is prepared and introduced intopressurized aluminum cans fitted with valves to control the discharge ofthe product from a foam nozzle.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.90 Sodiumhydroxide 0.41 Ammonia solution (28%) 6.25 Polyoxyethylene (4) laurylalcohol (Atlas Chemicals Brij 30) 0.23

Polyoxyethylene (23) lauryl alcohol (Atlas Chemicals Brij 35) 1.631,3-buty1ene glycol 2.30 Sodium silicate (Na O:SiO ratio of 3.22:1) 0.08Perfume 0.45

Monochlorodifluoroethane 3.40 Difiuoroethane 3.40 Distilled waterBalance Perfume and sodium silicate while having a desirable effect onthe packaged product are not essential to the success of the invention.The composition is found to give a pressure of about 55 p.s.i.g. at 70F. and about p.s.i.g. at F. Upon discharge from the container thecomposition appears as a foam which substantially collapses to a liquidwithin about 5 seconds. When the composition is used in waving hair,very satisfactory results are recognized over leading commercial wavingcompositions. The composition has the further advantage of being easy toapply to the hair without run off of excess lotion.

9 Example 6 [be following composition is prepared and introduced intopressurized cans fitted with valves to control the discharge of theproduct from a foam nozzle.

Perfume and sodium silicate while having a desirable effect on thepackaged product are not essential to the success of the invention. Thecomposition is found to give a pressure of about 55 p.s.i.g. at 70 F.and about 115 p.s.i.g. at 130 F. Upon discharge from the container thecomposition appears as a foam which substantially collapses to a liquidwithin about seconds. When the composition is used in waving hair, verysatisfactory results are recognized. The composition has the furtheradvantage of being easy to apply to the hair without run oif of excesslotion.

Any other propellant such as monochlorotrifluoromethane,trichloromonofiuoromethane, dichlorodifluoromethane,dichloromonofluorometihane, trichlorotrifiuoroethane,dichlorotetrafluoroethane, and difluoromonochloroethane may besubstituted for the above propellants of the example separately or insuitable combination with vapor pressure adjustment obtained byregulating the amounts of additives of the combinations for preparationof suitable fast-breaking foams without departing from the advantages ofthe invention.

It is to be understood that the foregoing detailed description is givenmerely by way of illustration and that many variations may be madetherein without departing from the spirit of this invention.

What is claimed is:

1. A two liquid phase pressurized hair waving composition adapted fordischarge from its container as a foam, which collapses to a liquidpromptly after discharge, consisting essentially of: from about 1% toabout of a member selected from the group consisting of thioglycolicacid, ammonium thioglycolate, and thioglycerol, an alkalizing agent asubstantial part of which is a base with a dissociation constant lessthan 10- imparting to the composition a pH above about 7 but below 10;from about 2 to about 20% by weight of a propellant selected from thegroup consisting of fluorinated, and chlorinated-fluorinated lowmolecular weight saturated aliphatic hydrocarbons represented by theformula C H Cl F wherein n represents a whole number 1 and 2; xrepresents zero, 1 to 4; y represents zero, 1 and 2; and'z represents 1to 4 and the sum of x, y and z is equal to 2n+2; from about 0.05% toabout 3 /2 by weight of a surface active agent selected from the groupconsisting of nonionic and anionic surface active agents; as apolyhydric alcohol from about 0.5% to about 5% by weight of an organiccompound selected from the group consisting of propylene glycol,1,3-butylene glycol, Z-methyl pentanediol-2,4, and mixtures thereof; andthe balance substantially water.

2. A pressure tight aluminum container which contains the composition ofclaim 1, said composition containing additionally as a corrosioninhibitor from about 001% to about 0.1% SiO added as 'water solublesodium silicate.

3. A two-liquid phase pressurized hair waving composition adapted fordischarge from its container as a foam, which collapses to a liquidpromptly after discharge, consisting essentially of: from about 3% toabout 6% of thioglycolic acid, an alkalizing agent, a substantial partof which is a base selected from the group consisting of ammonia,monoethanolamine, diethanolamine, tris- (hydroxymethyl) aminomethane,2-amino-2-methyl-l,3- propanediol and mixtures thereof imparting to thecomposition a pH in the range of 8.5 to 9.5; from about 2% to about 20%of a propellant selected from the group consisting ofdichlorodifluoromethane, dichlorotetrafluoroethane, difluoroethane andmonochlorodifluoroethane; from about 0.05% to about 3 /2% of a surfaceactive agent selected from the group consisting of nonionic and anionicsurface active agents; as a polyhydric alcohol from about 0.5% to about5% by weight of an organic glycol selected from the group consisting ofpropylene glycol, 1,3-butylene glycol, Z-methyl pentanediol-2,4, andmixtures thereof; and the balance substantially water.

4. A two liquid phase pressurized hair waving composition adapted fordischarge from its container as a foam, which collapses to a liquidpromptly after discharge, consisting essentially of: from about 1% toabout 10% of a member selected from the group consisting of thioglycolicacid, ammonium thioglycolate, and thioglycerol, an alkalizing agent asubstantial part of which is a base with a dissociation constant lessthan 10' imparting to the composition a pH above about 7 but below 10;from about 2% to about 20% by weight of a fluorinated, andchlorinated-fluorinated low molecular weight saturated aliphatichydrocarbon propellants; as a polyhydric alcohol from about 0.5% toabout 5% by weight of an organic compound selected from the groupconsisting of propylene glycol, 1,3-butylene glycol and 2-methylpentanediol-2,4 and mixtures thereof; from about 0.05 to about 3 /2% ofa surface active agent selected from the group consisting of nonionicand anionic surface active agents; and the balance substantially water.

5. A two liquid phase pressurized hair waving composition adapted fordischarge from its container as a foam, which collapses to a liquidpromptly after discharge consisting essentially of: from about 3% toabout 6% of thioglycolic acid, an alkalizing agent, a substantial partof which is a base selected from the group consisting of ammonia,monoethanolamine, diethanolamine, tris-(hydroxymethyl) aminomethane,2-amino-2-methyl-1,3-propanediol and mixtures thereof imparting to thecomposition a pH of about 9.3; as a propellant, not less than about 2.5%and not more than about 15% by weight of a propellant selected from thegroup consisting of fluorinated, and chlorinated-fiuorinated lowmolecular weight saturated aliphatic hydrocarbon propellants; as apolyhydric alcohol from about 1% to about 10% by weight of an organiccompound selected from the group consisting of propylene glycol,1,3-butylene glycol, Z-methyl pentanediol-2,4 and mixtures thereof; andfrom about 0.05% to about 3 /2% of a surface active agent selected fromthe group consisting of nonionic and anionic surface active'agents; andthe balance substantially water.

6. A pressure tight aluminum container which contains the composition ofclaim 5, said composition containing additionally as a corrosioninhibitor, from about 001% to about 0.1% SiO added as water solublesodium silicate.

7. A two liquid phase pressurized hair waving composition adapted fordischarge from its container as a foam, which collapses to a liquidpromptly after discharge, consisting essentially of: from about 3% toabout 6% of thioglycolic acid, an alkalizing agent a substantial part ofwhich is a base selected from the group consisting of ammonia,monoethanolamine, diethanolamine, tris- (hydroxymethyl) aminomethane,2-amino-2-methyl-1,3- propanediol and mixtures thereof imparting to thecomposition a pH of about 9.3; as a propellant, from about 2% to about20% of one selected from the group consisting ofdichlorodifiuoromethane, dichlorotetrafiuoroethane,

and difluoroethane and monochlorodifiuoroethane; as a polyhydric alcoholfrom about 1% to about 20% of an organic compound selected from thegroup consisting of propylene glycol, 1,3-butylene glycol, 2-methylpentanediol-'2,4 and mixtures thereof; and from about 0.05% to about 3/2% of a surface active agent selected from the group consisting ofnonionic and anionic surface active agents; and the balancesubstantially water.

8. A two liquid phase pressurized hair waving composition adapted fordischarge from its containers of foam which collapses to a liquidpromptly after discharge, consisting essentially of about 90% by weightof a waving lotion, comprising to 6 percent thioglycolic acid, 0.05 to0.5 percent sodium hydroxide, 4 to 7 percent ammonium hydroxide, 0.5 to2.0 percent a nonionic surface active agent, 0.5 to 5.0 percent1,3-butylene glycol and distilled water, and about by weight of apropellant selected from the group consisting ofdichlorodifluoromethane, dichlorotetrafiuoroethane,monochlorodifiuoroethane, and difluoroethane.

9. A two liquid phase pressurized hair waving composition adapted fordischarge from its containers of foam which collapses to a liquidpromptly after discharge, consisting essentially of about 90% by weightof a waving lotion, comprising 5 to 6 percent thioglycolic acid, 0.05 to0.5 percent sodium hydroxide, 4 to 7 percent ammonium hydroxide, 0.5 to2.0 percent a nonionic surface active agent, 0.5 to 5.0 percent 2-methylpropanediol-2,4 and distilled water, and about 10% by weight of apropellant selected from the group consisting ofdichlorodifluoromethane, dichlorotetrafluoroethane,monochlorodifiuoroethane, and difluoroethane.

10. A two liquid phase pressurized hair waving composition adapted fordischarge from its containers of foam which collapses to a liquidpromptly after discharge, consisting essentially of about by weight of awaving lotion, comprising 5 to 6 percent thioglycolic acid, 0.05 to 0.5percent sodium hydroxide, 4 to 7 percent ammonium hydroxide, 0.5 to 2.0percent a nonionic surface active agent, 0.5 to 5.0 percent propyleneglycol and distilled water, and about 10% by weight of a propellantselected from the group consisting of dichlorodifiuoromethane,dichlorotetrafluoroethane, monochlorodifiuoroethane, and difluoroethane.

References Cited UNITED STATES PATENTS 3,039,934 6/1962 Whitman et al.l67-87.l 3,099,603 7/1963 Banker et al. 167 -87.1

FOREIGN PATENTS 107,057 4/1939 Australia.

OTHER REFERENCES Lehne: American Perfumes and Cosmetics, vol. 78, No.10, pp. 103-107, October 1963.

Guillaume: German printed application N 8,064, August 1956.

ALBERT T. MEYERS, Primary Examiner.

VERA C. CLARKE, Assistant Examiner.

